Recovery of lignin from water and methanol using low-cost kaolin based tubular

ceramic membrane
Introduction -
This study investigated the performance of low-cost tubular ceramic membranes fabricated using
kaolin, quartz and calcium carbonate as inexpensive raw materials following the extrusion
method for lignin recovery from water and methanol. The use of additives in ceramic membrane
preparation is attractive as it improves the membrane properties such as mechanical strength and
chemical stability, etc. The additives can be categorized as binders, plasticizers, solvents,
dispersants, lubricants and wetting agents based on their functions. Binders connect precursor
materials in ceramic membranes by forming bridges, thereby enhancing their mechanical
strength. Several researches reported the use of carboxymethyl cellulose (CMC) as a binder due
to its excellent binding properties. In this work, kaolin based tubular ceramic membranes were
employed to investigate the recovery of lignin from solvents. The effect of different binder
(CMC) concentration on the properties of the tubular ceramic membrane was investigated, and
based on the characterization results, the most suitable membrane was chosen.
Materials And Method-
1) Membrane Preparation
Different batches of membranes with varying concentrations of carboxymethyl cellulose (1, 2
and 3 wt% solution) were prepared and tested in the present study. In this work, tubular
membranes were prepared with the outer diameter, inner diameter and length of 11.5, 5.5 and
100 mm, respectively. For making tubular shaped ceramic membranes, the inexpensive clay
powders were mixed manually until a homogenous mixture is obtained. A required amount of
CMC was weighed accurately and dissolved in 300 mL Millipore water with continuous stirring
to form a homogeneous solution. The solution was then slowly added to the mixture of the clay
powders and mixed properly until a dough type paste of desired consistency was obtained. The
paste was subsequently fed into an extruder, in which a piston was forced through a die to get
green tubular membranes. these extruded membranes were then subjected to four steps of heat
treatment for its continuous drying. In the first step, the membranes were air dried for 12 h at an
ambient room temperature (25 ◦C). In the second step, the membranes were dried at 100 ◦C for
12 h in a hot air oven. The third step involved drying of the membranes at a temperature of 200
◦C for 12 h in a box furnace. Following this heat treatment, the membranes were sintered in the
box furnace at 950 ◦C for 6 h at a heating rate of 0.5 ◦C/min. These controlled drying processes
decreased any possibility of thermal stress and maximized the removal of moisture. This sort of
confined heat treatment further reduces the formation of bends and cracks in the membrane. The
membranes thus obtained after the sintering process are hard and porous. These membranes were
then cut into 10 cm length and polished using abrasive paper of grade 220 to make its surface
smooth. For removing any free particles adhered onto the membrane surface during polishing,
the membranes were immersed in an Ultrasonic bath (Elma T460, India) with water for 15 min.
Finally, the obtained membranes were dried at 100 ◦C and used for further characterization.
2) Characterization of ceramic membranes- Various tests were performed to characterize
the sintered ceramic membranes prepared with 1, 2 and 3 wt% of CMC concentration.

3) Preparation of lignin solutions -Lignin-water solution (1000 mg/L) was prepared by

dissolving one gram of alkali black kraft lignin in one liter of Millipore water. Dissolution
of lignin present in the carob pods thus yielded the lignin-methanol solution in this study.
4) Microfiltration of lignin solution - For microfiltration of lignin-water/lignin-methanol
solution, experiments were conducted using the setup detailed earlier and by passing the
solution through the fabricated membrane at a constant cross flow rate of 50 LPH.
Permeate passing through the membrane was collected in the permeate tank, and the
permeate flux for all the five applied pressures (34􀀀 172 kPa) was calculated by
collecting the permeate samples after every 2 min. All the tests were carried out at room
temperature (25 ± 2 ◦C) and the following equation was used to calculate the percentage
rejection of lignin [3]: R(%) = [(Lfeed – Lpermeate)/ Lfeed ] × 100. Where Lfeed and Lpermeat are
lignin concentration in the feed and permeate, respectively, as determined by measuring
their absorbance at 412 nm using a UV–vis spectrophotometer
Result
 1) Microfiltration of lignin solutions- An increase in the permeate flux with
increasing pressure has been reported by other authors using ceramic membranes. As

observed previously in the case of pure methanol flux, a higher permeate flux is observed
with lignin-methanol solution than with lignin-water solution at all the applied pressure
values, which is due to a low viscosity of methanol. The percentage of lignin retention
decreased along with an increase in the applied pressure. In the case of lignin-water
solution, the percentage of lignin retention is found to be 82.8 % for an applied pressure
of 34 kPa. And for the lignin-methanol solution, it was 80 % for the same applied
 pressure. It is to be noted that the average pore size of the membrane used for lignin
separation is 0.180 μm. Hence, it is clear that the lignin separation by the prepared
membrane is primarily due to sieving mechanism, by which the lignin particles with a
size greater than the pore size of the membrane are retained by the membrane and the
remaining particles enter into the permeate stream.

Conclusion-

With an increase in the CMC concentration, porosity of the membranes decreased,

whereas the results of mechanical stability analysis portrayed an increase in its compressive
strength. In the microfiltration of the lignin-water and lignin-methanol solutions, the flux
declines due to membrane pore blocking by the lignin particles. Percentage lignin retention was
above 80 % from both the solutions at a very low applied pressure followed in the study.